Method of utilizing residue oils containing water



Feb. 18; 1930. H, MALLERY 7 1,747,375

METHOD OF UTILIZING RESIDUE OILS CONTAINING WATER Filed April 5. 1926 INVENTOR ATTORNEYfi Patented Feb. 1 1930 Ute ARLINGTON H. MALLERY, OE YORK, N. Y., ASSIGNOR ,TO MALLER-Y PROGESS CORPORATION, OF NEW YORK, N. Y., A CORPORATION OF DEL.AVU-LIIRJE METHOD OF UTILIZING RESIDUE OILS CONTAINING WATER Application filed April 5,

The present invention relates to a method for the utilization of residue oils and more particularly to a method of utilizing residue oils containing water, 'or h drocarbon oils,

emulsions, or acid sludges, composed of hydrocarbon oils, Water and acid and other materials.

In the production of gasoline from crude oils and other mineral oils, various oil resi- 10 dues are produced which are a source of great inconvenience and loss to the refiner, for the reason that no economical way has been devised for disposing of the residues and it has been the practice to store such residues by 5 allowing them to accumulate in a pond or excavated hole. The acid sludges-obtained by treating the distilled products from the mineral oil with acid, so as to remove unsaturated carbons and other impurities, are particularly obnoxious'on account of the odor and the tendency of formin emulsions which are almost impossible to break up. After the treatment of the various oil fractions with acid, fractions are generally washed with water to remove remaining amounts of acid and a part- '01 these washings are generally added to the acid sludge.

Many attempts have been made to devise a method by which the emulsions may be broken up so as to recover the oil therein, but such processes have been found 'to be costly and,'for certain refractory emulsions, have been found to bewholly inoperative.

As a result of a large number of experiments, I have discovered a method by which on residues containing water may be utilized and which is applicable to all grades of emulsions of oil and water up to substantially80% of Water. The method is, in fact, applicable to to emulsions containing even higher percentages of water, although it is doubtful whether oi'l emulsions containing such higher percentages of water may be economically treated. It is to be understood, however, that my 5 method is applicable to the treatment of all such emulsions. Furthermore, the method is particularly adapted forthe treatment of acid sludge and is of particular advantage in this connection for the reason that the sulphuric 50 acid, employed for washing mineral oils,

1926. Serial No. 99,938.

suitable purpose.

The primary object of the invention is to provide a method by which fluid fuels containing water maybe utilized and disposed of with profit.

Another object of the invention is to provide a method for burning combustible, material containing water in any proportion.

Another object of the invention is to provide a method for the "utilization of acid sludges in a manner so as to permit'recove'ry of the acid contained therein.

- Another object of the invention is topmvide a method by means of which miz'rturesv of oil residues and acid sludges may be utilized to obtain the heat value from the oil therein and to recover one or more valuable constituents as by-pr'od-ucts. I

A further object of the invention is to pro vide a method by means of which B. 8., roi'ly oil or heavy oil residues, mixed with acid sludge, or oil emulsions, may be burned to recover the heat values of the hydrocarbons contained therein, and whereby one or more of the inorganic constituents of the mixture may be recovered.

lVith these and other objects in view, the invention comprises the various features hereinafter more fully described an'd de'fin'ed in the claims. I

In carrying out the process of my invent'ion as applied to oil residues or other oil containing water, I preferably heat material to such a temperature that the wat'er is vaporized and the resultant steam may be su perheated. This maybe accomplished -in any suitable form of apparatus, such as a pipe coil, heated either by Waste gases *or by "an oil burner or in any other suitable way. I preferably heat the mixture under treatment to a temperature of approximately 1250" F, h although any temperature may be employed 95 whereby when air is passed to the burning mixture, the resulting temperature Will be at or above the kindling temperature of the oil in the resulting mixture. I find that as "a y practical lower limit the temperature should I peratures as high as 2000" F. may be satis-' be at least 900" F but the temperatureof the mixture may even exceed 1250'F., and temg factorily employed insome cases.

7 Attliis stage of the process, before air has been mixed with the gases, the oil in the mix- I ture'b'ecomes more or less cracked, whereby a large amount of heat is absorbed, the peration of cracking being an endothermic re- '-action. I maynow pass'th e resulting gases directly into" contact withair supplied in amounts suflicient to cause substantially complete combustion of the oil in the mixture.

TheJamount of air supplied should beregulated so as not to supply substantially more than is needed for complete combustiomzbe- "eauseofthe consequent loss of heat due to V the heating ofinert gasesinot lsfid'inthe re- .Isidered a total loss" to the By passing the gases-into contact with aflbody to be heated, such] as 'asteam in the residue employed is" accomplished without wasteofkheat; l q l r E i It is obvious that by this process the only loss of heat. involved inthe operation over thelusualmethod employed for the burning offuel oils, which contain no water, is that.

represented by the amount of heat, necessary to. vaporize the waterpresent'in'the oil which {is used, plus-the heat required to raisethe temperature ofthe waterfromthatof the 'residuef'oil mixture to a vaporizing tempera ture, and in. additionthepheat absorbed by the steam, which is formed from the water,

in raising itstemperature up to that of the gasesleaving the stack. By this process,ioil's containing water up to 80%may beutilized int-he manner described, theiamount of heat lost by the vaporization and; heating of the water. present in the residue or oil mixture is relatively smalhand is compensated for by.

tlieheat obtained from the cornbustionof the oil in the residue or oilfmixture. By this process, oils which haveheretofore been scone refiner may be satisfactorily utilized.

treatment of all oils containingwater, I have found thatthe vaporization ofthe oil and passed eitherin a continuous stream through the water sometimes causes more or less explosions or knocking may be substantially'eliminated; This knocking or'pounds .ing in lthe apparatus is due" apparently "to water'globules presentin the oil mixture or emulsion which are coatedor surrounded by afihnofoil which prevents the vaporization I not the water until the temperature has become so high that the vapor, tension of the water finally'breaks the oil film, and the water then flashes into. steam, causing the knocking sounder explosion? The severity: of, the

explosions or bursting water globules into steamj varies greatly with differenttypes of oils.

In cases in which oil emulsions are to be p r 1 treated which cause unusually violent explosions, or in cases in which theoilm-ixture to be employed isv more adapted to be treated lows: V ;i f t r I preferablypass'the oil emulsion or mix ture'of oil and water into contact with highly superheated steam, whereby the oil water 'mixture or'e'mulsion becomes distributed throughthe superheated steam, and becomes heated in such a manner as to reduce or water inv the oil. 3 The reason. for the, elimofiheating is notentirely understood, but it I by my. modified process, I proceed as folso V substantially avoid: the cracking sound or I V, knockingfduring the vaporization f-tlie .ination of the-fexplo'sionsby thisT node.

is possibleflthat the blanket of superheated steam, into which'the 1 oil mixure is passed, serves as a cushioning medlum during the time that the waterv globules becomeVapor- -ized, or it may bethat the surface tension of.

at ordinarytemperatures, ,or:preheated into if 7 contact with the superheated steam, or I- may I ifirst'vaporize the oil and'the water mixture and "thereafterpass superheated steam into contact with the vaporized. oil and water so as to attain a final temperature of the mix ture above 900 -F.,* or} preferably in the neighborhood of 1250 F., so that'when air is passed into contact with the .oil vapors'and the vapors have been ignited, the tempera-. i ture of combustion will be maintained above the kindling temperature.}i'By the above methods the' oil residues containing water,

or oilemulsions or mixtures containing Water may be continuouslytreated, whereby the various oil residu es at a refinery may; becontinuous'lyidisposed of, utilizinig the heat genw a I V erated fromtheresidues for the distillation V While the abovemethod is suitable forthe of oil," or for the be required.

The oil mixtures or generation of power asmay V emulsions may be superheated steam, theoil .and water vapors I being preferably passed or injected bymeans .stantially continuous.

of a valvemech'anism operating several times I A specific example of the mode ofcarrying out my inventionis describedjin connection with the accompanying dravving,;i hi h;

.; e fi u epr sen diagr ma iqa ly. an

apparatus for carrying out the invention.

Referring more particularly to the drawings, the numeral 2 designates a residue tank containing oil emulsion, or other liquid fuel containing water suspended in or otherwise admixed therewith. From the tank 2, the oil-water mixture is pumped by means of a pump 4 through a pipe 6, having a valve 8 therein for controlling the flow of the mixture and is passed into a pipe coil 10 or retort, which is heated by waste heat or by direct heat from any suitable source, the temperature of the retort or coil being preferably maintained at about 1000 F. and the pressure therein being preferably maintained at substantially lbs., although both the temperature and pressure may be varied con.- siderably as hereinbefore described. In the retort 10, the oil and water are vaporized and superheated whereby more or less cracking of the oil takes place, and probably more or less interaction takes place between the steam and the oil vapors formed. The products are heated inpassing through the retort so that at the time they leave the retort or coil they are at a temperature of substantially 1000 F. From the retort 10 the products formed therein are passed through a reducing valve 12 of any suitable form so that the pressure drops to substantially 10 lbs. in the conduit 14 to which they are passed. I have operated with pressures in the neighborhood also of 2 lbs. and 5 lbs. per square inch in the chamber or conduit 14 by means of which satisfactory operation was obtained. As, the products pass through the reducing valve 12, a fall in temperature occurs through expansion and I preferably heat the conduit or chamber 14 to about 1250 F. so as to supply heat to the products so as to maintain the temperature of the products above the kindling temperature, whereby when the products are burned with air the temperature necessary for combustion Will be maintained. The passage of the products into the conduit 14 may be continuous or intermittent as desired. In the chamber 14, I preferably supply superheated steam at about 1250 F., by means of the pipe 16, having a valve 18 therein which serves to regulate the supply of the steam. From the chamber 14 the mixture of gases and vapor is passed to the combustion chamber to which air is admitted through openings 20. The

amount of air for obtaining the proper comvan bustion may be regulated in any well known way.

In the treatment of oil mixtures carrying large quantities of water, I may add or mix therewith, if desired, other oil residues, such as fuel oil, in order to maintain substantially uniform conditions of operation or to increase the economy of the process.

I have found that my method is particularly adaptable for the treatment of acid sludges such as are obtained by the washing or treatment f vari us f actions 0 f Qil by means sf p ri i The s lphuri acid com: pounds which are formed with unsaturated hydrocarbons in the treatment of the oil fractions, comprise sulphonates, which are soluble in water and may thus be washed out of the O e va i u l s a gasol ne, ros e orlubricating oils, being as is well-known, insoluble in water. In the treatment of the various oil fractions with sulphuric acid, more r l a th s tur d hyd oca bons bec m mul i ed in the a id s u ge and a small amount are thus lflmQVed the sludge,

I preferably treat the sludge by one of the methods of treatment described above in con: nection with the treatment-ofres-idue .oils containing water. If the oil sludge contains a large proportion .of sulphuric acid, I may, if desired, omit the abstracting of the heat from the gases when combustion takes place and, instead of passing the'gases into contact with the steam boiler or other body to be heated, I may cool the gases directly by means of a condenser or other cooling'm'eans by which the water present in the gases, formed by the union of oxygen of the air with the combined hydrogen of the oil during combustion and also that which was originally present in the sludge, is separated out. Through the combustion of the oil, inert gases are formed, and the sulphur trioxide, and any sulphur dioxide formed in there: action, will be absorbed in the water present when the gases are passed through the con.- e rhe ga may i e r d, h Pass into contact with water from an outside source to absorb any remaining sulphur trioxide or sulphur dioxide in the gases issuing from the condenser. It is to be understood that I preferably abstract the heat from th as by Pas ng the gas s in o cont t with. a team b il r or ether b dy by mean of which the heat in the gases maybe utilized before abstracting sulphur trioxide for the e y f the Sulphuri acid rigi ally n the sludge. 7

Certain oil sludges which do not contain acid, pa ticul ly tho e ai by Wa mineral oil fractions with alkali,'may also be tr ate in the mann abov de ri ed, i iz ng th hea mbustion o the oi in'. the sludge by heating a boiler or still, or other device by means of which the heat is abstracted, but in this case the gases are permitted to escape into the atmosphere after the heat is abstracted therefrom' In a modification of my process, I may produce an oil gas, which is obtained by the incomplete combustion of residue oils containing water. The process which I preferably employ comprises heating the oil' and water under pressureat a temperature suflicient to change the water in the mixture to s pe he t d t am and supp ying an am unt.

' 1 the oil ancl water to pressure, imparting to v a heat-st uia eeiteer attmerthemates mer efi ei t i d i f nti l' y" b ve F, orahove the kindling temperature of the the mixture and'thenadrnitting' air to the foil in amounts" insufficient for complete "combustion;and-preferablyat such a 'rateas toform' {substantially all carbon monoxide I and little or no carbon dioxide 'frorn the coni hinedcarbon of the oil. Ifdesire d, heat'rnay I :16 be abstracted from the gases, resulting from the partialpcornhustiom, and the gases may the xpe' a eless ga mks' j' e s o rheans'untifl required for use.

' ti o -r n rs ood a l-im y-vi ii y 'anfrsuitablej apparatus for carrying out my proces j or processes and that various changes or :rnoclifications'r nay be made the various stagesfof the process withoutclepart ng from v the spiritorscope'oftheirWention as defined he un'clers'toodalso that myfprocess. is applicable not only to residue oils or? oil fractions" mifr ed with Water, but it ijsiequally applicable to crude oils containing ater or emulsions thereof, and may be used 7 for inineral oilsfor combustible materials in general admixed w th Water; It' nay loeiernployed forthe' disposalof sewage sludge containing'water,'or in] connection withresiclue.

tannin liquors, or for animal or vegetablefoil emulsions, onfish waste niaterial andin connectien Witlithe numerous waste products of various industries in which liquors contain is claimed asne'wis: :1 40

ing' coinbustihle inaterial Whichmust'be clis I i posed ofito'p'revent pollution of'stre'ams'and I 135' H I I for easons "o fsanit'ati'onJ Iolo not desire th'erefore to: limit thelscope of my invention exe'cpt as: hereinafter clefin'ecl the claims,

'teniperature of the coiiibustihle" material in \arnountto attain hustion, of the said material therein.

4. A method of utilizing emulsions contain-r 1m ing combustible Inaterial and Water; which COIlSlStS 1n confinlng the emulsionyprehm narily irnp'artingfto theeinulsion in it'scoh r fined state such-a quantity offhe'at as Will phangethe Water to steam, "the amount of heat supplied depending uponthe amount of "the mixture, and supplying air suificient r substantially co nplete co1n-- Water present anclithe calorific value of the I combustible material, and thereafter burn ing the material in the presence of air.

1 5. Ainethocl for utilizing'residue oils con- 3 c taining'. Water, which comprises subjecting the oil ancl w'ater to pressure, imparting to' the oil and Water "mixture While under pressu'i e' such a quantity of heat as will change the Water to superheated'steain, thereafter passing superheated steaminto the mixture at a'teniperature s'ufiic ent to raise the tenie perature of the mixture to the ignition ternperatu'reo'f thee-i1, and burning the mixture, 6." Amethod of utilizingeniulsions contain} ing' Water and combustible material, which 7 consists in -c'onfin'ing the emulsion, prelim-'- inarily heating the emulsion in'its confined i state so'as't'o supply sufficient heat'to render the emulsion combustible, raising the resultant products to the kindling'point of the com dbu stible material and thereafter burning the same in the presence of air.

Signed at New York; New York, this; 1st

day of April, 1926. r 1

ARLINGTON H. BIALLE RY Iiai7i11g thus describecl theinvention; What ineth of utilizing;emul'sions con} "tair ing comb'ustible; material and ater,

' eons ist'sfinicon fining the elnillsioniprelirn narily: mpart ngto the emulsion in'its,

li iil eeeu' i t l i a is An ethocljfor' utilizing residue miscontaining' waterg which coniprli'ses sub ectmg ioo theo'il and water While under pressure such a quantityfo f: lie at as ,Will cause the'water to be changed to superheated steam, passing air theretoinsufiicient aniount toattain substan- 'tially complete combustion of the oil fancl-l Qfburning theoil; l 7 P13. A method for utilizing acid sludgec0n- J56 taining combustible inaterialywhich":eoms

prises subjecting the sludge to pressure, im-

parting to the sludge while under pressure such a quantity ofheat'as will vaporize the 7 Water present, furnishing sufiicient heat to its maintain the-temperature above the kind-ling 

